U.S. patent application number 12/863804 was filed with the patent office on 2011-01-27 for wetting agents and dispersants, their preparation and use.
This patent application is currently assigned to BYK-Chemie GmbH. Invention is credited to Jurgen Omeis, Wolfgang Pritschins, Hans-Josef Teuwsen.
Application Number | 20110021699 12/863804 |
Document ID | / |
Family ID | 40626818 |
Filed Date | 2011-01-27 |
United States Patent
Application |
20110021699 |
Kind Code |
A1 |
Pritschins; Wolfgang ; et
al. |
January 27, 2011 |
WETTING AGENTS AND DISPERSANTS, THEIR PREPARATION AND USE
Abstract
The invention relates to addition compounds and their salts that
comprise polypropylene oxide structures, characterized in that the
addition compounds are obtainable by reacting (a) one or more
polyisocyanates having at least two isocyanate groups per molecule
with (b1) one or more compounds of the formula Y--XH, (b2)
optionally one or more compounds of the formula G-(XH).sub.n, (c1)
one or more compounds of the general formula Z-Q and (c2)
optionally one or more compounds of the general formula M-Q. The
invention further relates to the preparation of the addition
compounds and to their use as dispersants, wetting agents and
dispersion stabilizers, and also to solids coated with the addition
compounds.
Inventors: |
Pritschins; Wolfgang;
(Wesel, DE) ; Omeis; Jurgen; (Dorsten-Lembeck,
DE) ; Teuwsen; Hans-Josef; (Uedem, DE) |
Correspondence
Address: |
SCHWEGMAN, LUNDBERG & WOESSNER, P.A.
P.O. BOX 2938
MINNEAPOLIS
MN
55402
US
|
Assignee: |
BYK-Chemie GmbH
Wesel
DE
|
Family ID: |
40626818 |
Appl. No.: |
12/863804 |
Filed: |
February 19, 2009 |
PCT Filed: |
February 19, 2009 |
PCT NO: |
PCT/EP2009/001216 |
371 Date: |
October 12, 2010 |
Current U.S.
Class: |
524/875 ;
516/203; 524/871 |
Current CPC
Class: |
C08G 18/2875 20130101;
C08G 18/4833 20130101; C08G 18/4825 20130101; C08G 18/283
20130101 |
Class at
Publication: |
524/875 ;
524/871; 516/203 |
International
Class: |
C08L 75/04 20060101
C08L075/04; C08G 18/32 20060101 C08G018/32; B01F 17/16 20060101
B01F017/16 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 22, 2008 |
DE |
10 2008 010 705.0 |
Claims
1. Addition compounds and salts thereof, wherein the addition
compounds are obtainable by reacting (a) one or more
polyisocyanates having at least two isocyanate groups per molecule
with (b1) one or more compounds of the formula (Ia) Y--XH (Ia)
where XH is a group that is reactive towards isocyanates and Y is a
monomeric or polymeric group that is not reactive towards
isocyanates, that contains no tertiary amino groups and that
comprises one or more aliphatic, cycloaliphatic and/or aromatic
groups, that may optionally contain the heteroatoms O, S, Si and/or
N and/or ether, urethane, carbonate, amide, siloxane and/or ester
groups, and, wherein hydrogen may optionally be replaced by
halogen; the compound of the general formula (Ia) possessing a
number-average molar mass M.sub.n of less than 20 000 g/mol and at
least 55 mol % of the compounds of the formula (Ia) possessing a
number-average molecular weight M.sub.n of 150 to 10 000 g/mol and
which represent XH-functionalized polyalkylene oxides which contain
40 to 100 mol % of alkylene oxide units having at least three
carbon atoms, based on the total amount of alkylene oxide units,
with the proviso that 20% to 90% of the isocyanate groups of
component (a) are reacted with the compounds of the formula (Ia),
(b2) one or more compounds of the formula (Ib) G-(XH).sub.n (Ib)
where n is 2 to 4 and G is an aliphatic, cycloaliphatic and/or
aromatic group which contains at least 2 carbon atoms, has no
tertiary amino groups and has a number-average molecular weight
M.sub.n of not more than 3000, reacted in an amount such that 0% to
60% of the isocyanate groups of the polyisocyanates originally used
are reacted, with the proviso that, as a result of the reactions
(b1) and (b2), a total of at least 20% and not more than 90% of the
isocyanate groups of the polyisocyanates originally used have
undergone reaction, (c1) one or more compounds of the general
formula (IIa) Z-Q (IIa) in which Q is --NH.sub.2, --NHR or OH, in
which R is a linear or branched alkyl group having 1 to 18 carbon
atoms, and Z is an organic basic radical having at least one
tertiary amino group and containing no isocyanate-reactive groups,
and (c2) optionally one or more compounds of the general formula
(IIb) M-Q (IIb) in which Q is --NH.sub.2, --NHR or OH, in which R
is a linear or branched alkyl group having 1 to 18 carbon atoms,
and M is an organic radical having a number-average molar mass of
not more than 1000 g/mol, with at least one tertiary amino group
and at least one hydroxyl group, with the proviso that at least 10%
of the isocyanate groups of component (a) are reacted with
component (c1).
2. The addition compounds according to claim 1, where Y contains,
the heteroatoms O, S, Si and/or N and/or ether, urethane,
carbonate, amide, siloxane and/or ester groups, and, wherein
hydrogen is replaced by halogen.
3. The addition compounds according to claim 1, where Z has one or
more of the following definitions: A) an aliphatic and/or
cycloaliphatic group having at least one tertiary amino group, or
B) a heterocyclic group having at least one basic ring nitrogen
atom that does not contain a hydrogen atom, it being possible for
the heterocyclic group to be attached to the group Q via an organic
coupling group.
4. The addition compounds according to claim 1, where at least two
different compounds of the formula (Ia) are used.
5. The addition compounds and salts thereof according to claim 1
wherein some of the monofunctional compounds of the formula (Ia)
are monohydroxy-functional polyethers, polyesters,
polyether-polyesters and/or aliphatic and/or cycloaliphatic
monoalcohols having 2 to 30 carbon atoms, some of whose hydrogen
atoms have been replaced by halogen and/or aryl radicals.
6. The addition compounds according to claim 1, wherein di-, tri-
or tetrahydroxy-functional polyethers, polyesters or
polyether-polyesters are used as polyfunctional compounds of the
formula (Ib).
7. The addition compounds according to claim 1, wherein they
contain no unsaturated groups.
8. The addition compounds according to claim 1, wherein the
polyisocyanates are products, containing one or more isocyanurate
groups, of diisocyanates based on hexamethylene diisocyanate,
diisophorone diisocyanate and/or tolylene diisocyanate.
9. A process for preparing the addition compounds according to
claim 1, comprising reacting (a) one or more polyisocyanates having
at least two isocyanate groups per molecule with (b1) one or more
compounds of the formula (Ia) Y--XH (Ia) where XH is a group that
is reactive towards isocyanates and Y is a monomeric or polymeric
group that is not reactive towards isocyanates, that contains no
tertiary amino groups and that comprises one or more aliphatic,
cycloaliphatic and/or aromatic groups, that may optionally contain
the heteroatoms O, S, Si and/or N and/or ether, urethane,
carbonate, amide, siloxane and/or ester groups, and, wherein
hydrogen may optionally be replaced by halogen; the compound of the
general formula (Ia) possessing a number-average molar mass M.sub.n
of less than 20 000 g/mol and at least 55 mol % of the compounds of
the formula (Ia) possessing a number-average molecular weight
M.sub.n of 150 to 10 000 g/mol and which represent
XH-functionalized polyalkylene oxides which contain 40 to 100 mol %
of alkylene oxide units having at least three carbon atoms, based
on the total amount of alkylene oxide units, with the proviso that
20% to 90% of the isocyanate groups of component (a) are reacted
with the compounds of the formula (Ia), (b2) one or more compounds
of the formula (Ib) G-(XH).sub.n (Ib) where n is 2 to 4 and G is an
aliphatic, cycloaliphatic and/or aromatic group which contains at
least 2 carbon atoms, has no tertiary amino groups and has a
number-average molecular weight M.sub.n of not more than 3000
g/mol, reacted in an amount such that 0% to 60% of the isocyanate
groups of the polyisocyanates originally used are reacted, with the
proviso that, as a result of the reactions (b1) and (b2), a total
of at least 20% and not more than 90% of the isocyanate groups of
the polyisocyanates originally used have undergone reaction, (c1)
one or more compounds of the general formula (IIa) Z-Q (IIa) in
which Q is --NH.sub.2, --NHR or OH, in which R is a linear or
branched alkyl group having 1 to 18 carbon atoms, and Z is an
organic basic radical having at least one tertiary amino group and
containing no isocyanate-reactive groups, and (c2) optionally one
or more compounds of the general formula (IIb) M-Q (IIb) in which Q
is --NH.sub.2, --NHR or OH, in which R is a linear or branched
alkyl group having 1 to 18 carbon atoms, and M is an organic
radical having a number-average molar mass of not more than 1000
g/mol, with at least one tertiary amino group and at least one
hydroxyl group, with the proviso that at least 10% of the
isocyanate groups of component (a) are reacted with component
(c1).
10. The process for preparing an addition compound according to
claim 9, where first of all component (a) is reacted with component
(b1) and, where appropriate, (b2), and then a reaction takes place
with component (c1).
11. The process for preparing an addition compound according to
claim 9, where component (a) is reacted first with compounds of the
general formula (Ia) where n is 1 and then with compounds of the
general formula (Ib) where n is 2 to 4.
12. Use of one of the addition compounds of claim 1, prepared by
the process according to claim 9 as a dispersant, dispersion
stabilizer and/or wetting agent.
13. Use of one of the addition compounds of claim 1, prepared by
the process according to claim 9 in the preparation or processing
of paints, inks, including printing inks, paper coatings, leather
and textile colours, pastes, pigment concentrates, ceramics,
cosmetic preparations, casting compositions and/or moulding
compositions based on synthetic, semi-synthetic or natural
macromolecular substances.
14. Use of one of the addition compounds of claim 1, prepared by
the process according to claim 9 for preparing pigment- and/or
filler-comprising pigment concentrates, paints, pastes and/or
moulding compositions.
15. Use of one of the addition compounds of claim 1, prepared by
the process according to claim 9 for coating solids in powder
particle and/or fibre particle form.
16. Use of an addition compound according to claim 15, the solids
in powder particle and/or fibre particle form being dispersible
pigments and/or fillers.
17. Use of one of the addition compounds of claim 1, prepared by
the process according to claim 9 for preparing a pigmented
paint.
18. Use of an addition compound of claim 1, prepared by the process
according to claim 9 for producing a pigmented coating on a
substrate, the addition compound being used to prepare a pigmented
paint, the pigmented paint being applied to the substrate, and the
pigmented paint applied to the substrate being baked or cured or
crosslinked.
19. Solids in powder particle and/or fibre particle form, wherein
they are coated with an addition compound of claim 1, prepared by
the process according to claim 9.
20. Solids in powder particle and/or fibre particle form according
to claim 19, the solids in powder particle and/or fibre particle
form being pigments and/or fillers.
Description
[0001] The present invention relates to addition compounds and
salts thereof that are suitable as wetting agents and dispersants
and as dispersion stabilizers. The invention further relates to
processes for preparing these addition compounds, to their use as
wetting agents and dispersants and dispersion stabilizers for
organic and inorganic pigments and also fillers in organic and
aqueous systems, and to pulverous or fibrous solids coated with
such wetting agents and dispersants and amenable to incorporation
into liquid systems.
[0002] In solution or dispersion in a liquid, wetting agents lower
the surface tension or interface tension and in that way increase
the wetting capacity of the solution. Dispersants are suitable in
general for stabilizing particulate solids in binders, paints,
pigment pastes, plastics and plastics blends, for reducing the
viscosity of such systems, and for improving the flow properties.
Dispersion stabilizers are suitable in general for stabilizing
dispersions that have already been produced.
[0003] In order to be able to incorporate solids into liquid media,
high mechanical forces are necessary. It is usual to use
dispersants in order to lower the dispersing forces and in order to
minimize the total input into the system of energy needed to
deflocculate the particulate solids, and hence also to minimize the
dispersing time. Dispersants of this kind are surface-active
substances of anionic, cationic or neutral structure. These
substances, in a small amount, are either applied directly to the
solid or added to the dispersing medium. It is also known that,
following complete deflocculation of the agglomerated solids into
primary particles, after the dispersing operation, there are also
instances of reagglomeration, thereby completely or partly
nullifying the dispersing effort. As a consequence of the
inadequate dispersing and/or as a result of reagglomeration there
are unwanted effects, such as viscosity increase in liquid systems,
shade drift and losses of gloss in paints and coatings, and a
reduction of mechanical strength in plastics.
[0004] A multiplicity of different substances are nowadays used as
dispersants for pigments and fillers. Besides simple compounds of
low molecular mass, such as lecithin, fatty acids and their salts,
and alkylphenol ethoxylates, for example, complex structures, too,
are used as dispersants. Such structures especially include
amino-functional and amide-functional systems, which find broad use
within the dispersants. In EP 158 406 and EP 208 041 use is made,
for example, for the purpose of dispersing pigments, of amino- and
amide-functional poly- and oligocopolymers based on polyamines and
polycaprolactones, in which all the reactive amino groups have been
converted into amide groups. These products, however, constitute
complex reaction mixtures which are difficult to reproduce and have
very poor solubilities in solvents and inadequate compatibilities
with binders and other resins.
[0005] Good results can already be achieved with polymeric
dispersants based on polyisocyanates, as are described for example
in EP 0 154 678 A1 or EP 0 318 999 A2.
[0006] EP 0 154 678 A1 describes dispersants which are obtained by
addition of monohydroxy compounds with polyisocyanates. The
monohydroxy compounds contain at least one aliphatic,
cycloaliphatic or aromatic group of at least one --O-- and/or
--COO-- group. The monohydroxy compounds are preferably polyesters.
In particular, polyesters formed from aliphatic lactones and
aliphatic monoalcohols are employed. As a further compound for
addition with polyisocyanates it is preferred to use di- or
trifunctional polyethylene glycols.
[0007] In EP 0 318 999 A2 the addition compounds known from EP 0
154 678 A1 were modified by the additional incorporation of
silicone-containing and/or urethane-containing groups. The
resultant dispersants have more universal compatibility.
[0008] WO 2006/132910 A2 describes polyurethane-based dispersants
which are composed of a linear polyurethane main chain with various
possible side chains. The compounds described are characterized in
that they contain at least one or, preferably, two or more reactive
carbon-carbon double bonds per molecule. Consequently the
compounds, after the dispersing operation, can be crosslinked
either through Michael addition of polyamines or else through
free-radical reaction.
[0009] EP 0 335 197 A1 discloses polyisocyanate polyaddition
compounds which act as dispersants. They are prepared using, among
other components, polyesters or, in particular, polyethylene
oxides.
[0010] EP 0 731 148 A2 discloses the use of polyisocyanate addition
products which contain hydrophilic polyether chains as suitable
dispersants for the incorporation of solids into aqueous coating
materials. The dispersants are prepared from the reaction of 5-100
equivalent-% (based on the isocyanate groups of the isocyanate
component) of a monohydric alcohol component (B) and also, where
appropriate, three further, optional components with a
polyisocyanate. The monohydric alcohol component (B) is composed of
at least one monohydric polyether alcohol having an ethylene oxide
unit content of 50% to 99.5% by weight, which may be modified by
addition reaction with epsilon-caprolactone in an amount of up to
40% by weight, based on the weight of the monohydric alcohol.
[0011] In EP 0 826 753 A1, dispersants comparable with those of EP
0 731 148 A2 are prepared in a solvent-free way. In this case, as a
difference, 0 to 75 equivalent-% of the ethylene oxide-based
monofunctional polyether component (B), where appropriate with
modification with epsilon-caprolactone, is used. In addition there
may be three further, optional components reacted with the
isocyanate component. The polymers of the pigment formulation that
are disclosed in EP 0 827 973 A1 also contain high fractions of
ethylene oxide in the polyalkylene oxide fraction.
[0012] WO 1997/26984 A1 describes reaction products of
polyisocyanates with a component Y--R--X. In the component Y--R--X
the hydroxyl- or amino-functional group X is attached via the
bridge R to a nitrogen-containing heterocycle Y in such a way that
a nitrogen atom of the heterocycle forms a tertiary amine with the
bridge R. The addition of the tertiary amines Y--R--X with
polyisocyanates produces dispersants which are used in compositions
with high solids content.
[0013] US 2004/0242727 A1 discloses special radiation-curable
dispersants for producing tack-free inks and coatings. The
compounds in question are the reaction products of polyisocyanates
with at least one radiation-curable component, preferably with
(meth)acrylates, especially polycaprolactone acrylates, and one or
more further components.
[0014] US 2004/0260013 A1 discloses dispersants with acidic groups
which are composed of a linear polyurethane backbone of low
molecular mass diisocyanates with side chains composed of
poly(C.sub.2-C.sub.4)alkylene oxides. Of the alkylene oxide side
chains, at least 60%, preferably 70% or even 80% by weight, based
on the total weight of the alkylene oxides, must have been
synthesized from ethylene oxide units.
[0015] DE 101 59 315 A1 describes dispersants which are obtainable
from diisocyanates and which contain an alkyl-capped oligoalkylene
oxide radical. The oligoalkylene oxide radical necessarily
comprises one or more ethylene oxide groups and may in addition
also contain a further, branched alkyl radical, although this is
not preferred.
[0016] WO 2004/104064 A2 concerns a dispersant comprising low
molecular mass diisocyanates for non-aqueous systems, said
dispersant being composed of a linear polyurethane backbone with
polyester, polyether and/or polyacrylate side chains.
[0017] But the dispersants presented above often represent only
partial solutions to the problems depicted at the outset. On
account of numerous possible side reactions in the course of their
preparation, many of these products represent very complex and
poorly defined reaction mixtures, with the resulting disadvantages,
such as very restricted compatibilities and poor solubilities.
Consequently these reactions can be carried out only in highly
dilute solutions, and the end products have very low solids
contents of, in general, below 50% and in many cases even only
20-30%. The large quantities of solvent that are consequently
introduced by way of these products, however, lead to considerable
problems in modern coating systems, since, as part of the ongoing
efforts to produce environmentally compatible systems, there is a
need to reduce the amount of solvent as far as possible (e.g. in
the case of pigment concentrates, high-solids and ultra-high-solids
coatings), or even to abandon organic solvents entirely. Products
which contain polyester radicals based on hydroxycarboxylic acids
and/or their lactones, such as epsilon-caprolactone and/or
delta-valerolactone, are problematic on account of their
crystallization tendency, and exhibit problems with poor solubility
and compatibility. Particularly in the case of decorating paints
based on aromatic-free white spirits, the dispersants of the prior
art can be used either not at all or only with restrictions, owing
to poor compatibility.
[0018] In view of the multiplicity of organic and inorganic
pigments and filling materials that are used today, sufficient
stabilization of the particulate solids to be dispersed, by
desorption-stable occupancy of the surface, is not adequately
ensured. Consequently there are instances of agglomeration, since
the efficient steric shielding that is necessary is lacking.
[0019] On account of the high quantities of such dispersants that
are used, relative to the solids to be dispersed (in the case of
carbon black, up to 100% of dispersant relative to pigment), it is
frequently the case in the finished coating film that there are
impairments affecting the intercoat adhesion and the resistance
properties, especially water resistance, solvent resistance and
scratch resistance.
[0020] The present invention is therefore based on the object of
eliminating the above-described disadvantages of known dispersants,
in other words of developing additives which, while effectively
stabilizing pigments or fillers, lower the millbase viscosity of
the paints, pastes or plastics formulations to an extent such that
processing with a high degree of filling is possible, without
detriment to the resistance properties of the cured coatings. At
the same time, especially in the case of pigment pastes and filler
pastes, a broad compatibility must be ensured, so that they can be
used in many different binders and coating materials. Furthermore,
it is necessary for the dispersing additives of the invention that
are used to allow the pastes, or the binders prepared with these
pastes, to be mixed with one another without flocculation.
[0021] A further aim is to provide dispersing additives which also
act as wetting agents. Lastly, the additives provided ought also to
act as dispersion stabilizers, especially as emulsion
stabilizers.
[0022] Furthermore, the intention is that the addition compounds
provided in accordance with the invention should solve the problems
associated with the incorporation of lactones into the dispersants
of the prior art. High fractions of lactone, especially
caprolactone, frequently lead, as already described above, to
partially crystalline compounds with a high viscosity, something
which adversely affects the processing properties especially in the
case of the production of pigment pastes and filler pastes. Such
lactone-based dispersants also possess the solubility problems
outlined above. Similar disadvantages are also known for
dispersants which contain very high polyethylene oxide
fractions.
[0023] These addition compounds, furthermore, are of surprisingly
broad usefulness both in polar and in apolar binder systems. They
strongly lower the viscosity of the millbase during dispersing and
so make it possible to prepare formulations having a high solids
fraction.
[0024] Surprisingly it has become apparent that a marked
improvement in the resistance properties in conjunction with
effective dispersing and stabilizing of pigments or filler
particles in binders, pigment pastes or plastics formulations can
be achieved if the addition compounds of the invention, described
below, are used.
[0025] The objective is achieved through the provision of addition
compounds and salts thereof which are obtainable by reacting [0026]
(a) one or more polyisocyanates having at least two isocyanate
groups per molecule with [0027] (b1) one or more compounds of the
formula (Ia)
[0027] Y--XH (Ia) [0028] where [0029] XH is a group that is
reactive towards isocyanates and [0030] Y is a monomeric or
polymeric group that is not reactive towards isocyanates, that
contains no tertiary amino groups and that comprises one or more
aliphatic, cycloaliphatic and/or aromatic groups, [0031] the
compound of the general formula (Ia) possessing a number-average
molar mass M.sub.n of less than 20 000 g/mol and [0032] at least 55
mol % of the compounds of the formula (Ia) possessing a
number-average molecular weight M.sub.n of 150 to 10 000 g/mol
[0033] and which represent XH-functionalized polyalkylene oxides
which contain 40 to 100 mol % of alkylene oxide units having at
least three carbon atoms, based on the total amount of alkylene
oxide units, [0034] with the proviso that 20% to 90% of the
isocyanate groups of component (a) are reacted with the compounds
of the formula (Ia), [0035] (b2) one or more compounds of the
formula (Ib)
[0035] G-(XH).sub.n (Ib) [0036] where n is 2 to 4 and G is an
aliphatic, cycloaliphatic and/or aromatic group which contains at
least 2 carbon atoms, has no tertiary amino groups and has a
number-average molecular weight M.sub.n of not more than 3000, and
which can contain --O--, --COO--, --CONH--, --S-- and/or
--SO.sub.2-- groups, are reacted in an amount such that 0% to 60%,
preferably 0 to 45% and more preferably 0 to 40% of the NCO groups
of the polyisocyanates originally used are reacted, [0037] with the
proviso that, as a result of the reactions (b1) and (b2), a total
of at least 20% and not more than 90%, preferably 30 to 65% and
more preferably 40 to 60% of the isocyanate groups of the
polyisocyanates originally used have undergone reaction, and [0038]
(c1) one or more compounds of the general formula (IIa)
[0038] Z-Q (IIa) [0039] in which Q is --NH.sub.2, --NHR or OH, in
which R is a linear or branched alkyl group having 1 to 18 carbon
atoms, and [0040] Z is an organic basic radical having at least one
tertiary amino group and containing no isocyanate-reactive groups,
and [0041] (c2) optionally one or more compounds of the general
formula (IIb)
[0041] M-Q (IIb) [0042] in which Q is --NH.sub.2, --NHR or OH, in
which R is a linear or branched alkyl group having 1 to 18 carbon
atoms, and [0043] M is an organic radical having a number-average
molar mass of not more than 1000 g/mol, with at least one tertiary
amino group and at least one hydroxyl group, [0044] with the
proviso that at least 10% of the isocyanate groups of component (a)
are reacted with component (c1).
Component (a)
[0045] For preparing the addition compounds of the invention use is
made as component (a) of polyisocyanates having at least two
isocyanate groups per molecule. Isocyanates of this kind are known
from the prior art in the present technical field.
[0046] The compounds in question are more preferably oligomeric or
polymeric derivatives of monomeric diisocyanates that contain
biuret, urethane, uretdione and/or isocyanurate groups. Monomeric
diisocyanates of this kind are, for example,
1,4-diisocyanatobutane, hexamethylene diisocyanate (HDI),
2-methyl-1,5-diisocyanatopentane,
1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or
2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane,
1,3- and 1,4-diisocyanatocyclohexane, 1,3- and
1,4-bis(isocyanatomethyl)cyclohexane,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
(isophorone diisocyanate, IPDI),
4,4'-diisocyanatodicyclohexylmethane, tolylene diisocyanate (TDI),
1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane,
bis(isocyanatomethyl)norbornane and 1,3- and
1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI) or mixtures of such
diisocyanates. Alternatively, the stated monomeric isocyanates may
be used as they are, alone or in a mixture, or in a mixture with
their oligomeric or polymeric derivatives containing biuret,
urethane, uretdione and/or isocyanurate groups. In accordance with
the invention it is possible to use one or more monomeric,
oligomeric or polymeric polyisocyanates.
[0047] The polyisocyanates must possess an average functionality of
at least 2. The average functionality is preferably at least 2.5
and more preferably at least 3. Particular preference is given to
the above-described derivatives of HDI, TDI and/or IPDI, and
especially those of TDI.
[0048] Examples of polyisocyanates of this kind are those which are
obtainable, for example, by addition of diisocyanates with polyols,
such as Desmodur L from Bayer, or those obtainable by biuret
reaction from diisocyanates, such as the commercial product
Desmodur N from Bayer, or else the polyisocyanates with an
isocyanurate parent structure that are obtainable by cyclization of
diisocyanates, such as the commercial products Desmodur HL and
Desmodur IL from Bayer, the commercial products Polurene KC or
Polurene HR from SAPICI, or trimeric isophorone diisocyanate
(isocyanurate T1890 from Chemische Werke Huls). Further examples of
polyisocyanates available as commercial products are Desmodur VL
(polyisocyanate based on diphenylmethane diisocyanate (MDI), Bayer
AG), Desmodur Z4370 (polyisocyanate based on isophorone
diisocyanate (IPDI), Bayer AG), Desmodur N3400 (aliphatic HDI
uretdione, Bayer AG), Thanecure T9 (aromatic TDI uretdione, TSE
Industries), Crelan VP LS 2147 and Crelan VP LS 2347 (aliphatic
IPDI uretdiones, Bayer AG), Polurene KD (polyisocyanurate based on
tolylene diisocyanate (TDI), SAPICI), Uronal RA.50
(polyisocyanurate based on TDI, from Galstaff), Polurene A
(polyisocyanate based on TDI trimethylolpropane (TMP), SAPICI),
Polyurene MC (polyisocyanate based on TMP-IPDI, SAPICI), Polyurene
MD.70 (polyisocyanate based on TMP-TDI-MDI, SAPICI). These
commercial products are frequently not in the pure form of a
polyisocyanate, but instead in the form of mixtures of
polyisocyanates of similar structure. As polyisocyanates in the
present invention it is preferred to use trimerization
products--that is, products containing one or more isocyanurate
groups--of diisocyanates based on hexamethylene diisocyanate (HDI),
isophorone diisocyanate (IPDI) and/or tolylene diisocyanate
(TDI).
[0049] By the abovementioned "average functionality of at least 2"
is meant that in terms of the isocyanate groups the commercial
products have the stated functionality of at least 2.
"Functionality of 3", for example, means that a molecule contains
on average 3 free isocyanate groups.
[0050] The average functionality can be determined experimentally
by determining the number-average molecular weight M.sub.n and the
NCO number as described in the example section of the present
invention, and calculating therefrom the NCO equivalent weight. The
average functionality is the ratio formed from the number-average
molecular weight and the NCO equivalent weight. Preferably the
average molecular weight of the polyisocyanates is at least 200,
more preferably at least 300, very preferably at least 500.
Preferably the average functionality is 2.5 to 10, more preferably
at least 3, such as 3 to 6, for example.
Component (b1)
[0051] The polyisocyanates of component (a) are reacted in
accordance with the invention with compounds of component (b1) of
the above formula (Ia).
[0052] The compounds of the formula (Ia) are characterized in that
they contain exactly one group XH that is reactive towards
isocyanate groups. The compounds of the formula (Ia) react
irreversibly via their reactive XH group with the isocyanates.
[0053] For the Y group of the compound of the general formula (Ia),
it is the case that it is not reactive towards isocyanates, i.e.
that they contain no active hydrogen atoms according to
Zerewitinoff. This means in particular that the group Y is free
from the above-mentioned groups XH.
[0054] Examples of XH are OH, NH.sub.2, NHR, SH or COOH, R being a
branched or unbranched alkyl group having 1 to 18 carbon atoms.
Preferably XH is OH, NH.sub.2 or NHR. With particular preference
these functional groups are hydroxyl groups, since these compounds
are readily obtainable and/or available commercially and the
resulting reaction products are highly soluble in solvents which
are employed in the context of the later use of the additives in
accordance with the invention.
[0055] The groups Y that are not reactive towards isocyanates may
contain the heteroatoms O, S, Si and/or N and/or ether, urethane,
carbonate, amide and/or ester groups. In the groups Y it is
possible for halogen, preferably fluorine and/or chlorine, to be
substituted for hydrogen.
[0056] As compounds of the formula (Ia) it is possible to use
aliphatic, cycloaliphatic and/or araliphatic compounds. It is also
possible to use mixtures of such compounds, in other words at least
two different compounds of the formula (Ia). The aliphatic or
araliphatic compounds of the formula (Ia) may be straight-chain or
branched. They may be saturated or unsaturated. Saturated compounds
are preferred, however.
[0057] Examples of compounds of the formula (Ia) are straight-chain
or branched alcohols such as methanol, ethanol, butanol,
ethylhexanol, decanol, isotridecyl alcohol, lauryl alcohol, stearyl
alcohol, isobornyl alcohol, benzyl alcohol, propargyl alcohol,
oleyl alcohol, linoleyl alcohol, oxo-process alcohols, neopentyl
alcohol, cyclohexanol, fatty alcohols, alkylphenols, monophenyl
diglycol, alkylnaphthols, phenylethanol, hydroxy-functional vinyl
compounds such as, for example, hydroxybutyl vinyl ether,
hydroxy-functional acrylates or methacrylates such as, for example,
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl
(meth)acrylate, and also polyolefin polyols, such as unhydrogenated
or hydrogenated, hydroxy-functional polybutadienes, polypropylenes,
ethylene/butylene copolymers or polystyrenes having an average
functionality of 1 to 3. Examples of corresponding commercial
products are the hydroxy-terminated hydrogenated polybutadienes,
available under the name Polytail.RTM. from Mitsubishi Chemical, or
the hydroxy-terminated ethylene/butylene copolymers Kraton.RTM.
Liquid L-1203, L-1302 and L-2203 from Kraton Polymers, or the
liquid polybutadienes available as NISSO-PB from Nippon Soda Co.,
or the saturated, long-chain, linear, largely primary alcohols
available from Baker Petrolite as Unilin.RTM. alcohols, having
chain lengths of up to C.sub.50 and molecular weights of 375 to 700
g/mol, and their ethoxylates, which are obtainable under the
Unithox.RTM. name. Further examples are described inter alia in
EP-A-154 678. Of the aforementioned hydroxy compounds, those
containing no polymerizable double bonds are preferred.
[0058] As compounds of the formula (Ia) it is also possible to use
those which contain ester, ether, urethane, carbonate, amide and/or
siloxane groups or combinations of these groups. They may
therefore, for example, be polyethers, polyesters, polyurethanes,
polycarbonates, polysiloxanes or, for example, mixed
polyether-polyesters.
[0059] Polyesters can be prepared for example by reacting
dicarboxylic acids and also their esterifiable derivatives such as,
for example, anhydrides, acid chlorides or dialkyl esters such as
dimethyl esters or diethyl esters by reaction with diols and mono.
The esterification may be carried out in bulk or else by means of
azeotropic esterification in the presence of an entraining agent.
Examples of dicarboxylic acids are succinic acid, maleic acid,
fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic
acid, phthalic acid or dimerized fatty acids and their isomers and
hydrogenation products. Examples of diols are as follows: ethylene
glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, cis-1,2-cyclohexanedimethanol,
trans-1,2-cyclohexanedimethanol, and also polyglycols based on
ethylene glycol and/or propylene glycol.
[0060] Polyesters of the formula (Ia) may also be those which can
be obtained by polycondensation of one or more, optionally
alkyl-substituted, hydroxy carboxylic acids and/or ring-opening
polymerization of the corresponding lactones such as propiolactone,
valerolactone or caprolactone, for example, by means of a
monohydroxy starter component, as described in EP-A-154 678 (U.S.
Pat. No. 4,647,647). If used, preferably they possess a
number-average molecular weight M.sub.n of 150 to 5000 g/mol. As a
starter component it is possible in principle to use any compounds
other than those given as compounds of the formula (Ia). The
monofunctional alcohols used as starter components possess
preferably 1 to 30, more preferably 4 to 14, carbon atoms.
Mentioned by way of example are n-butanol, longer-chain, saturated
and unsaturated alcohols, such as propargyl alcohol, oleyl alcohol,
linoleyl alcohol, oxo-process alcohols, cyclohexanol,
phenylethanol, neopentyl alcohol, ethylene glycol, propylene glycol
and glycerol, but also fluorinated alcohols, hydroxy-functional
polydialkylsiloxanes, hydroxy-functional vinyl compounds such as,
for example, hydroxybutyl vinyl ether, hydroxy-functional acrylates
or methacrylates such as, for example, hydroxyethyl acrylate,
hydroxyethyl methacrylate, hydroxybutyl (meth)acrylate, and
hydroxy-functional polyalkylene glycol acrylates and methacrylates.
It is also possible to convert alcohols of the above-described kind
and substituted and unsubstituted phenols, by alkoxylation in
accordance with known processes, using alkylene oxides such as, for
example, ethylene oxide, propylene oxide, butylene oxide and/or
styrene oxide, into polyoxyalkylene monoalkyl, polyoxyalkylene
monoaryl, polyoxyalkylene monoaralkyl and polyoxyalkylene
monocycloalkyl ethers and to use these hydroxy polyethers in the
manner described above as starter components for the lactone
polymerization. In each case it is also possible to use mixtures of
the aforementioned compounds, examples being lactone mixtures, of
.epsilon.-caprolactone and .delta.-valerolactone, for example. The
lactone polymerization is carried out by known methods, initiated
by BF.sub.3, p-toluenesulphonic acid or dibutyltin dilaurate, for
example, at temperatures of about 70.degree. C. to 180.degree. C.
Preferably, however, component (b1) contains less than 35 mol % of
compounds of the formula (Ia) which contain copolymerized lactones
or their hydroxycarboxylic acid analogues. With particular
preference their fraction is less than 20 mol %. With very
particular preference component (b1) contains no compounds of the
general formula (Ia) that contain copolymerized lactones or their
hydroxycarboxylic acid analogues.
[0061] Preferred compounds of the formula (Ia) are
hydroxy-functional polyethers, hydroxy-functional polyesters,
hydroxy-functional polyether-polyesters and/or aliphatic and/or
cycloaliphatic alcohols having 2 to 30 carbon atoms, some of whose
hydrogen atoms may have been replaced by halogen and/or aryl
radicals.
[0062] As compounds of the formula (Ia) it is also possible to use
monofunctional polysiloxanes such as, for example, monoamino- or
monohydroxy-functional polydialkyl-siloxanes containing hydroxyl
groups not attached to silicon atoms, or to use
aminoalkylpolysiloxanes, which where appropriate may have been
polyether-modified and/or polyester-modified. In this case the
respective amino-functional compounds carry primary or secondary,
but not tertiary, amino groups. It is preferred to use
hydroxyalkylpolydimethylsiloxanes having number-average molecular
weights M.sub.n of 400 to 8000 g/mol, more preferably 400 to 5000
g/mol and very preferably 400 to 2000 g/mol.
[0063] As compounds of the formula (Ia) it is also possible to use
polyurethanes, polyether-polyurethanes, polyester-polyurethanes
and/or polyether-polyester-polyurethanes, which can be obtained by
addition reaction of diisocyanates with dihydroxy compounds in the
presence of monofunctional starter components.
[0064] As a diisocyanate for synthesizing the compounds of the
formula (Ia) that contain urethane groups it is possible to use the
aliphatic, cycloaliphatic and/or aromatic diisocyanates known per
se from polyurethane chemistry and having 4 to 15 carbon atoms,
such as tetramethylene, hexamethylene, trimethylhexamethylene,
dodecamethylene, isophorone, tolylene and diphenylmethane
diisocyanates, methylenebis(4-cyclohexyl isocyanate) or
1,4-cyclohexanebis(methyl isocyanate). As hydroxy compounds for
synthesizing the compounds of formula (Ia) that contain urethane
groups it is preferred to use diols having 2 to 12 carbon atoms,
polyoxyalkylene glycols and dihydroxy-functional polyesters having
preferred number-average molecular weights M.sub.n of not more than
2000 g/mol. As monohydroxy-functional starter component it is
possible to use alcohols having up to 30 carbon atoms, such as
already described for preparing the polyesters of formula (Ia), but
also the hydroxy polyesters and hydroxy polyethers that are
described as a compound of formula (Ia). The polyesters preferably
have a number-average molecular weight M.sub.n of 300 to 5000
g/mol, and the polyethers one of 200 to 2000 g/mol.
[0065] The radical Y can also contain carbonate groups such as are
obtained by reaction with open-chain and/or cyclic carbonates in
accordance with the prior art. Suitability is possessed for example
by carbonate-modified linear polyesters or polycarbonate diols such
as are used in preparing polyurethane. Examples are described in
U.S. Pat. No. 4,101,529, EP 0358 555, or WO 02/085507. Suitable
carbonates are, for example, aliphatic, cycloaliphatic, araliphatic
and/or aromatic esters of carbonic acid, such as dialkyl carbonates
such as dimethyl carbonate, diethyl carbonate or diphenyl
carbonate, for example, catechol carbonate or cyclic alkylene
carbonates. Particular suitability is possessed by cyclic alkylene
carbonates having 5- or 6-membered rings, which if desired may be
substituted. Preferred substituents are aliphatic, cycloaliphatic
and/or aromatic groups having up to 30 carbon atoms. Examples of
suitable cyclic alkylene carbonates are ethylene carbonate,
propylene carbonate, glyceryl carbonate, trimethylene carbonate,
4-methyltrimethylene carbonate, 5-methyltrimethylene carbonate,
5,5-dimethyltrimethylene carbonate, 5,5-diethyltrimethylene
carbonate or 5-methyl-5-propyltrimethylene carbonate.
[0066] The radical Y may carry further groups which behave inertly
during the formation of the adduct, such as, for example, the
carboxamide group (--NHCO--), unactivated double bonds or urea
moieties (--NHCONH--). The fraction of the compounds of the formula
(Ia) that carry such groups should preferably be below 40 mol %,
more preferably below 5 mol %, based on all of the compounds used
of the formula (Ia). Particularly preferred compounds are those
containing none of these groups at all.
[0067] The ester, ether, urethane, carbonate and/or siloxane groups
that may be present can be in a block structure (for example
poly(ethylene oxide-block-propylene
oxide-block-epsilon-caprolactone), form a gradient or else be
arranged randomly.
[0068] As a compound of the formula (Ia) it is also possible to use
polyacrylic esters and/or polymethacrylic esters having on average
one isocyanate-reactive group, such as are obtained by anionic,
cationic or free-radical polymerization of acrylic esters and/or
methacrylic esters. Preference is given to monohydroxy-functional
compounds. Monohydroxy-functional polyacrylic esters and
polymethacrylic esters are those containing on average one hydroxyl
group in the molecule. Such compounds have already been used in
this field of the art for preparing other dispersants, as are
described for example in U.S. Pat. No. 4,032,698 or EP 318 999.
Such polyacrylates have preferably a number-average molecular
weight M.sub.n of 300 to 20 000 g/mol, more preferably 500 to 10
000 g/mol. They can be arranged in a block structure or else
randomly or form a gradient.
[0069] The carboxyl group of the monomeric acrylates and/or
methacrylates can be esterified with, for example, aliphatic,
cycloaliphatic and/or aromatic alcohols such as methanol, butanol,
cyclohexanol, 2-ethylhexanol, lauryl, stearyl, isobornyl or benzyl
alcohol or with ether alcohols such as 2-methoxyethanol,
2-phenoxyethanol, tetrahydrofurfuryl alcohol, or glycidol, with
polyester alcohols such as hydroxy-functional polycaprolactone, or
with alkoxypolyalkylene glycols such as methoxypolyethylene glycol
or methoxypolypropylene glycol. Methoxypolypropylene glycols are
preferred as alkoxypolyalkylene glycols. The number-average
molecular weight M.sub.n of the esterification component is
preferably below 2000 g/mol. For preparing the hydroxy-functional
polyacrylates and/or polymethacrylates it is also possible to use
mixtures of different monomers described above. For preparing these
polyacrylates and/or polymethacrylates it is also possible as
comonomers to use vinyl esters such as vinyl acetate, vinyl ethers
such as vinyl ethyl ether, styrene, vinyltoluene and/or
vinylcyclohexane. The resulting copolymers have been synthesized
from preferably not more than 50 mol % of comonomers that have no
acrylic functionality.
[0070] Also possibly functioning as compound of the formula (Ia)
are hydroxy-functional poly-2-alkyl-2-oxazolines or
poly-2-alkyl-2-oxazines. Monohydroxy-functional compounds are used
with preference. As the person skilled in the art is aware,
poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines are obtained
by cationic, ring-opening polymerization of 2-alkyl-2-oxazolines or
2-alkyl-2-oxazines with initiators such as para-toluenesulphonic
acid, methyl tosylate or methyl triflate, for example. The
oxazolinium or oxazinium end groups that result from the living
cationic polymerization mechanism can be converted by alkaline
hydrolysis via amino ester end groups into the more stable hydroxy
amides. An alternative route to the preparation of
monohydroxy-functional poly-2-alkyl-2-oxazolines or
poly-2-alkyl-2-oxazines is the polymerization with
2-(4-hydroxyphenyl)-N-methyl-2-oxazolinium
trifluoromethanesulphonate as the initiating species (A. Gro.beta.,
G. Maier, O, Nuyken, Macromol. Chem. Phys. 197, 2811-2826 (1996)).
Through the choice of the alkyl substituent it is possible to
control the compatibility: for example, the water-solubility of
poly-2-ethyl-2-oxazoline makes it suitable for highly polar
systems, whereas poly-2-lauryl-2-oxazoline, for example, is
compatible in apolar systems. Where block copolymers are formed
from 2-ethyl-2-oxazoline and 2-lauryl-2-oxazoline, the polymers are
notable for a particularly broad compatibility. Such
poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines possess
preferably a number-average molecular weight M.sub.n of 300 to 20
000 g/mol, more preferably 500 to 10 000 g/mol.
[0071] As compounds of the formula (Ia) it is also possible to use
mono-XH-functional polyalkylene oxides. These can be obtained, for
example, by alkoxylating the other compounds described as compounds
of the formula (Ia), such as alkanols, cycloalkanols, phenols or
the above-described hydroxy polyesters, with alkylene oxides such
as ethylene oxide, propylene oxide, butylene oxide, styrene oxide
or mixtures thereof. In the case of mixed polyethers, they may be
arranged randomly, as a gradient or in blocks. These polyethers
advantageously have a number-average molecular weight (M.sub.n) in
the range from about 100 to 10 000, preferably from 150 to 5000 and
more preferably from 200 to 3500 g/mol. Preference is given to
polyethers based on ethylene oxide, propylene oxide, and also
butylene oxide and mixtures thereof. Further preferred are
monohydroxy-functional polyoxyalkylene monoalcohols such as allyl
polyethers, for example Polyglycol A 350, Polyglycol A 500,
Polyglycol A 1100, Polyglycol A 11-4, Polyglycol A 20-10 or
Polyglycol A 20-20 from Clariant AG or Pluriol.RTM. A 010 R,
Pluriol.RTM. A 11 RE, Pluriol.RTM. A 13 R, Pluriol.RTM. A 22 R or
Pluriol.RTM. A 23 R from BASF AG, vinyl polyethers, for example
Polyglycol V 500, Polyglycol V 1100 or Polyglycol V 5500 from
Clariant AG, polyoxyethylene monoalcohols prepared starting from
methanol, such as Pluriol.RTM. A 350 E, Pluriol.RTM. A 500 E,
Pluriol.RTM. A 750 E, Pluriol.RTM. A 1020 E, Pluriol.RTM. A 2000 E
or Pluriol.RTM. A 5010 E from BASF AG, polyoxypropylene
monoalcohols prepared starting from alkanol, such as Polyglycol
B01/20, Polyglycol B01/40, Polyglycol B01/80, Polyglycol B01/120 or
Polyglycol B01/240 from Clariant AG or Pluriol.RTM. A 1350 P or
Pluriol.RTM. A 2000 P from BASF AG, and polyalkoxylates started
using different fatty alcohols and having a variable degree of
alkoxylation, of the kind known to the skilled worker under the
trade names Lutensol.RTM. A, Lutensol.RTM. AT, Lutensol.RTM. AO,
Lutensol.RTM. TO, Lutensol.RTM. XP, Lutensol.RTM. XL, Lutensol.RTM.
AP and Lutensol.RTM. ON from BASF AG. Preference is given to using
polyoxyalkylene monoalcohols which contain ethylene oxide and/or
propylene oxide and/or butylene oxide groups and which may have
been modified with styrene oxide. Particular preference is given to
using polyoxyalkylene monoalcohols such as, for example, Polyglycol
B 11/50, Polyglycol B 11/70, Polyglycol B 11/100, Polyglycol B
11/150, Polyglycol B 11/300 or Polyglycol B 11/700 from Clariant
AG, Pluriol.RTM. A 1000 PE, Pluriol.RTM. A 1320 PE, or Pluriol.RTM.
A 2000 PE from BASF AG or Terralox WA 110 from DOW Chemicals, which
are polyoxyalkylenes prepared starting from butanol, formed from
ethylene oxide and propylene oxide, and with a terminal OH group.
Of the aforementioned compounds, preference is given to those which
contain no polymerizable double bonds.
[0072] Component (b1) must contain at least 55 mol %, preferably at
least 75 mol % and more preferably 100 mol % of compounds of the
general formula (Ia) which are XH-functionalized polyalkylene
oxides and which possess a number-average molecular weight M.sub.n
of 150 to 10 000 g/mol, preferably at least 300 g/mol, more
preferably at least 600 g/mol and very preferably at least 1000
g/mol. The upper limit for the maximum molecular weight M.sub.n is
preferably not more than 5000 g/mol, more preferably not more than
3000 g/mol, and very preferably not more than 2000 g/mol. These
compounds must contain alkylene oxide units with at least three
carbon atoms in an amount of 40 to 100 mol %, preferably at least
55 mol %, more preferably at least 60 mol %, very preferably at
least 65 mol % and, in one particularly preferred embodiment, 100
mol %, based on the total amount of alkylene oxide units. The
alkylene oxide units having at least three carbon atoms derive
preferably from propylene oxide and butylene oxide. Particular
preference is given to the use of polypropylene oxide-based
compounds, and very particular preference to monohydroxy-functional
polypropylene oxides prepared starting from butanol. A suitable
comonomer having less than three carbon atoms is ethylene oxide.
These compounds are prepared preferably, as described in the
preceding section, by alkoxylation of monohydroxy-functional
starter compounds. They preferably contain no polyester fractions,
in particular no polyester fractions derived from lactones or
hydroxy carboxylic acids, and are preferably free from
polymerizable double bonds.
[0073] In applications requiring a broad compatibility, as in the
universal paste sector, for example, it is frequently advantageous
to use addition compounds which are prepared with mixtures of
different compounds of the formula (Ia). Where, for example, the
addition compounds of the invention are to be used in universal
tinting pastes for aqueous and apolar systems, a combination of
water-soluble with apolar compounds of the formula (Ia) is an
advantage.
[0074] The number-average molecular weight M.sub.n of the compound
Y--XH is smaller than 20 000 g/mol and is preferably not more than
10 000 g/mol, more preferably not more than 5000 g/mol, very
preferably not more than 3500 g/mol, and better still not more than
2000 g/mol. The minimum molecular weight M.sub.n of Y--XH is
preferably 100 g/mol, more preferably 150 g/mol, very preferably
200 g/mol, and most preferably 400 g/mol. Preferably less than 50
mol % of the compounds used of formula (Ia) ought to possess a
number-average molecular weight of less than 100 g/mol, more
preferably less than 25 mol %, very preferably less than 15 mol %
and most preferably 0 mol %.
[0075] In the reaction with the monofunctional compounds of the
formula (Ia), 20% to 90%, preferably 20% to 70% and more preferably
25% to 60% of the free NCO groups originally used are reacted.
Component (b2)
[0076] The compounds of the general formula (Ib) G-(XH).sub.n with
n=2 to 4 differ from those of the formula (Ia) essentially in that
they contain two, three or four functional groups XH, defined
independently of one another, which are reactive towards
isocyanates. Of the groups XH, those which are preferred are the
same as under formula (Ia). The number-average molecular weight
M.sub.n of the compounds of the formula (Ib) is less than 3000
g/mol and it is preferably not more than 2500 g/mol, more
preferably not more than 2000 g/mol, very preferably not more than
1500 g/mol. The minimum molecular weight M.sub.n of compounds of
the formula (Ib) is preferably 100 g/mol, more preferably 150
g/mol, very preferably 300 g/mol and ideally 600 g/mol.
[0077] Examples of di-, tri- and tetra-functional compounds of the
formula (Ib) are diols, triols and tetraols and, respectively,
diamines, triamines and tetramines without tertiary amino groups
having 2 to 12 carbon atoms, dihydroxydialkyl sulphides and
dihydroxy sulphones. Examples are butanediol, hexanediol,
cyclohexanedimethanol, neopentyl glycol, ethylene glycol, glycerol,
trimethylolpropane, pentaerythritol fatty acid dialkanol amides,
thiodiglycol di(4-hydroxyphenyl) sulphone, and also
hydroxy-functional polybutadienes having an average functionality
of 2 to 3. One preferred group of compounds of the formula (Ib) are
polyoxyalkylene glycols more preferably having alkylene groups
having 2 to 4, very preferably with two, carbon atoms, and
preferably having number-average molecular weights M.sub.n in the
range from 200 to 2000 g/mol and more preferably 400 to 1500 g/mol.
Ethoxylates with 3 hydroxyl groups are obtained, for example, by
polymerization using trifunctional alcohols as a starter component.
Preferred polyoxyalkylene glycols are polyethylene glycols.
[0078] As di-, tri- or tetra-functional compounds of the formula
(Ib) it is also possible to use those which can be obtained by
polymerizing one or more lactones, as already mentioned, by means
of di-, tri- or tetrahydroxy starter components. Preferably these
polyesterpolyols have a number-average molecular weight M.sub.n of
500 to 2000 g/mol. A preferred starter component is butanediol or
ethylene glycol. Also suitable, however, are the abovementioned
diols, triols or tetraols as starter components. Preferably
component (b2) contains less than 50 mol %, more preferably less
than 20 mol % and very preferably no polyester polyols, in
particular no polyester polyols based on lactones or their
hydroxycarboxylic acid analogues.
[0079] As polyfunctional compounds of the formula (Ib) it is also
possible to use polyurethanes, polyether-polyurethanes,
polyester-polyurethanes and/or polyether-polyester-polyurethanes,
which can be obtained by addition reaction of a diisocyanate with a
dihydroxy compound in analogy to the corresponding monofunctional
compounds according to formula (Ib). Preferably these
urethane-containing compounds according to formula (Ib) have an
average functionality of not more than 2 and a number-average
molecular weight of 300 to 2500 g/mol, preferably of 500 to 1500
g/mol.
[0080] The di-, tri- or tetra-functional compounds of the formula
(Ib) produce crosslinking between the reaction products of
polyisocyanate and monofunctional compounds of the formula (Ia).
The starting products can be used for example in amounts such that
the di-, tri- or tetra-functional compounds of the formula (Ib)
constitute the centre of the molecule, and such that attached to
them are the polyisocyanates whose remaining isocyanate groups have
been or are reacted with monofunctional compounds of the formula
(I). It is of course also possible for a certain overcrosslinking
or undercrosslinking to be present.
[0081] In the case of the reaction with the di-, tri- or
tetra-functional compounds of the formula (Ib) it is the case that
0% to 60%, preferably 0% to 45% and more preferably 0% to 40% of
the NCO groups originally used are reacted.
[0082] Particularly preferred products are obtained entirely
without the use of di-, tri- or tetra-functional compounds of the
formula (I).
[0083] In total at least 20%, more preferably at least 25%, and not
more than 90%, preferably not more than 80%, more preferably not
more than 70%, of the NCO groups of the component (a)
polyisocyanate that were originally used are reacted with the
compounds of the formula (I).
[0084] The reaction of the polyisocyanates with different compounds
of the formulae (Ia) and (Ib) can be carried out in one single
reaction step or in two or more reaction steps in succession. This
can take place in any order. In many cases, however, it is
advantageous to react the polyisocyanate in succession with the
components in the order first of monofunctional compounds (formula
(Ia)) and then of polyfunctional compounds (formula (Ib)). The
isocyanate addition can take place, depending on the reactivity of
the individual reactants, within the temperature range that is
customary for this kind of reaction, from room temperature up to
about 150.degree. C. For the purposes of acceleration and reduction
of side reactions it is possible to use the customary prior art
catalysts such as tertiary amines, for example triethylamine,
di-methylcyclohexylamine, N-methylmorpholine,
N,N'-di-methylpiperazine, 2-(dimethylaminoethoxy)ethanol,
di-azabicyclo[2.2.2]octane and similar compounds, and also, in
particular, organometallic compounds such as titanic esters, for
example, iron compounds such as iron(III) acetylacetonate, for
example, tin compounds, such as tin diacetate, tin dioctoate, tin
dilaurate or the dialkyl derivatives of tin dialkyl salts of
aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin
dilaurate or the like. These catalysts are customarily used in
amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of
polyisocyanate.
Component (c1)
[0085] Component (c1) is represented by the general formula (IIa)
as Z-Q. The group Z is an organic basic radical having at least one
tertiary amino group that contains no NCO-reactive groups. The
radical Z is preferably an aliphatic or cycloaliphatic group having
at least one tertiary amino group, where appropriate in the form of
a tertiary ring nitrogen atom of a heterocyclic ring system. The
tertiary amino group, or the heterocyclic ring system with tertiary
ring nitrogen, may be attached to the group Q directly or via an
organic bridging group ("spacer"). The spacer via which the
tertiary amino group or the heterocyclic ring system with tertiary
ring nitrogen may be attached to the group Q comprises preferably 2
to 10, more preferably 2 to 5, carbon atoms. With particular
preference it is an alkylene group having 2 to 10, very preferably
2 to 5, carbon atoms, or a polyether group having the same number
of carbon atoms. The group Q stands for NH.sub.2, OH or NHR, in
which R stands for a linear or branched alkyl group having 1 to 18
carbon atoms.
[0086] One group of compounds which can be used as compounds Z-Q of
the formula (IIa) is composed of monohydroxy amines having a
tertiary amino group, or aliphatic diamines having a tertiary amino
group and a primary or secondary amino group, such as, for example,
(N,N-diethylamino)ethanol, (N,N-dimethylamino)ethanol,
(N,N-dimethylamino)propanol, 2-(diethylamino)ethylamine,
3-(dimethylamino)propylamine, 3-(diethylamino)propylamine,
N,N-diethyl-1,4-butanediamine, 1-diethylamino-4-aminopentane, of
which 3-(dimethylamino)propylamine and (N,N-diethylamino)ethanol
are preferred.
[0087] In the case of a further group, Z is a monocyclic or
bicyclic heterocyclic group, of which a ring nitrogen atom is
attached to the group Q preferably via an alkylene group having 2
to 5 carbon atoms. Preferred heterocycles are triazole, pyrimidine,
imidazole, pyridine, morpholine, pyrrolidine, piperazine,
piperidine, benzimidazole, benzothiazole and/or triazine and more
preferably imidazole and benzimidazole. These heterocycles may
contain one or more substituents. They preferably carry one of the
following groups: alkyl and/or alkoxy groups having 1 to 6,
preferably 1 to 4 carbon atoms (in which case a methoxy group is
preferred), or tertiary amino groups.
[0088] It is preferred that the heterocyclic groups are attached
via a ring nitrogen atom and an alkylene group, preferably with 2
to 5 carbon atoms, to the group Q. The heterocyclic group may of
course, besides this ring nitrogen atom, also contain further
heteroatoms, including further ring nitrogen atoms.
[0089] Further examples of the compounds of the formula (IIa) are
N-(3-aminopropyl)imidazole, N-(3-aminopropyl) morpholine,
N-(2-aminoethyl)piperidine, 1-methylpiperazine,
aminoethylpiperazine. It is characteristic of these compounds that
they contain per molecule at least 1 reactive group with at least 1
Zerewitinoff hydrogen atom which is able to react with the NCO
groups, and that they additionally possess a nitrogen-containing
basic group without reactive hydrogen. These basic groups are
characterized in the prior art by their pKa value (cf. U.S. Pat.
Nos. 3,817,944; 4,032,698 and 4,070,388). Preference is given to
compounds with basic groups having a pKa value of 2 to 14, more
preferably of 5 to 14 and very preferably of 5 to 12. The pKa value
can be taken from tabular works. The limiting values indicated
above refer to the measurement of the pKa value at 25.degree. C. in
a 0.01 molar concentration in water. These basic groups likewise
endow the addition compounds of the invention with basicity.
[0090] Compounds of the formula Z-Q can be obtained, for example,
by reacting a (meth)acrylate or epoxide with an amine or
nitrogen-containing heterocyclic ring system. Examples of reaction
products between a (meth)acrylate and a nitrogen-containing
heterocyclic ring system are the reaction products of the
hydroxyethyl esters and hydroxypropyl esters of (meth)acrylic acid
with the nitrogen-containing heterocyclic ring structure, the
following structural elements being attached to the nitrogen of the
heterocyclic ring structure:
-propionic acid 2-hydroxyethyl ester, -propionic acid
2-hydroxypropyl ester, -2-methylpropionic acid 2-hydroxyethyl ester
and -2-methylpropionic acid 2-hydroxypropyl ester, and ethoxylated
and/or propoxylated derivatives thereof. The acrylic esters are
preferred.
[0091] The reaction with amines proceeds analogously.
[0092] Through reaction of an epoxide with an amine or with a
nitrogen-containing heterocyclic compound it is likewise possible
to prepare the compounds Z-Q. In the course of the reaction, the
group Q formed is a secondary hydroxyl group, and a tertiary amino
group is formed on the nitrogen atom that takes part in the
reaction.
Component (c2)
[0093] Compounds M-Q according to formula (IIb) that are used are
compounds in which M is an organic radical having a number-average
molar mass of not more than 1000 g/mol, preferably not more than
500 g/mol and more preferably 300 g/mol, containing at least one
tertiary amino group and at least one OH group, and in which Q is
NH.sub.2, NHR or OH (where R is a linear or branched alkyl group
having 1 to 18 carbon atoms).
[0094] M preferably contains 1 to 10, more preferably 1 to 5 and
very preferably 1 to 3, such as for example 2, OH groups. Primary
OH groups are preferred.
[0095] Examples of M-Q with tertiary amino groups and OH groups are
triethanolamine, N-methyldiethanolamine,
aminopropylmethylethanolamine, 3-(diethylamino)propane-1,2-diol,
tetrakis(2-hydroxypropyl)ethylenediamine,
bis(2-hydroxyethyl)dodecylamine and bis(2-hydroxyethyl)
octadecylamine.
[0096] The compounds of component (c2) can be prepared in analogy
to the compounds of component (c1) by reaction of (meth)acrylates
or epoxides with amines. Where, for example, glycidol is employed
as the epoxide, which already contains a primary hydroxyl group,
then, by reaction with a secondary amine, a tertiary amine and a
secondary hydroxyl group are formed additionally, and so such
adducts carry a primary and a secondary hydroxyl group and also a
tertiary amino group.
[0097] Nitrogen-containing heterocycles can be reacted analogously
with (meth)acrylates and epoxides.
[0098] For preparing the addition compounds of the invention, it is
also possible to use mixtures of different starting materials such
as mixtures of (a) polyisocyanates and/or components (b1) and/or
(b2) and/or components (c1). Individual representatives of the two
or more components (a), (b1), (b2) or (c1) may be used in a
superstoichiometric or substoichiometric amount. The proportions,
however, are preferably chosen such that the isocyanate groups
undergo substantially complete reaction; this means that preferably
at least 90%, more preferably at least 95%, very preferably at
least 98%, and ideally all of the isocyanate groups have undergone
reaction.
[0099] By virtue of the basic groups the addition compounds are
capable of forming salts. For the purposes of the invention, as
dispersants, they can also be used in the form of the corresponding
salts. In certain cases, by means of such partial or complete
salination it is possible to obtain an improvement in activity
and/or an enhanced solubility or compatibility. Even in
applications where the basicity of the products is a disrupting
factor, as for example, in acid-catalysed systems, it is frequently
possible to achieve improvements by means of partial or complete
neutralization.
[0100] The salts are obtained from the resultant reaction product
by neutralization with one or more organic or inorganic acids or by
quaternization. The amount of acid to be used is guided by the
field of use. Depending on each individual case, the acid
components may be used in equimolar, substoichiometric or
super-stoichiometric amounts. From polycarboxylic acids, for
example, it is also possible to use up to one equivalent of
polycarboxylic acid per basic group to be neutralized in order to
give the products an acidic character. It is preferred to carry out
approximately equimolar neutralization. Preference is given to
salts with organic carboxylic acids or acidic phosphoric esters.
Examples of such acidic phosphoric esters are given in EP 893 155,
EP 417 490 and U.S. Pat. No. 5,143,952. Examples of carboxylic
acids are aliphatic and/or aromatic carboxylic acids such as
short-chain or long-chain fatty acids, formic acid, acetic acid,
neodecanoic acid, oleic acid, tall oil fatty acid, stearic acid,
ricinoleic acid, natural saturated or unsaturated plant or animal
fatty acids and their maleic anhydride adducts, maleic acid,
fumaric acid, succinic acid, dodecenylsuccinic acid,
5-norbornene-2,3-dicarboxylic acid, adipic acid, glutaric acid,
benzoic acid, nitrobenzoic acid, phthalic acid, tetrahydrophthalic
acid, isophthalic acid, terephthalic acid, dimerized or trimerized
fatty acids, citric acid and abietic acid.
[0101] The addition compounds of the invention preferably contain
no ethylenically unsaturated groups.
[0102] Furthermore, the addition compounds of the invention are
preferably prepared from components which are not lactone-based,
especially not caprolactone-based; in other words, from components
(a), (b1), optionally (b2), (c1) and optionally (c2), which have
themselves been prepared without the use of any lactones, in
particular no caprolactones (or the corresponding hydroxycarboxylic
acid).
[0103] When the polyisocyanates whose use is preferred are employed
that have on average at least 2.5 free isocyanate groups, branched,
i.e. non-linear, polyurethane structures are formed. Accordingly,
non-linear addition compounds are particularly preferred in
accordance with the invention.
[0104] The preparation of the addition compounds of the invention
can be carried out, according to viscosity, in bulk or in the
presence of suitable solvents, solvent mixtures or other suitable
carrier media. Suitable solvents or carrier media are all those
which are not reactive under the chosen reaction conditions or
whose reactivity towards the coreactants is negligible and in which
the reactants and the reaction products are at least partly
soluble. Examples are hydrocarbons such as toluene, xylene,
aliphatic and/or cycloaliphatic benzine fractions, chlorinated
hydrocarbons such as chloroform, trichloroethane, cyclic and
acyclic ethers such as dioxane, tetrahydrofuran, polyalkylene
glycol dialkyl ethers such as dipropylene glycol dimethyl ether,
esters of monocarboxylic, dicarboxylic or polycarboxylic acids,
such as ethyl acetate, butyl acetate, butyrolactone, dimethyl
2-methylglutarate, triacetin, phthalates or other plasticizers, di-
or polycarboxylic esters, dialkyl esters of C.sub.2 to C.sub.4
dicarboxylic acids, referred to as "Dibasic Esters", alkyl glycol
esters such as ethyl glycol acetate, methoxypropyl acetate, ketones
such as methyl isobutyl ketone, cyclohexanone, acetone, acid amides
such as dimethylformamide, N-methylpyrrolidone, and the like. The
solvent or solvents and/or carrier media are advantageously
selected to take account of the planned field of use. For example,
for addition compounds of the invention for use in water-thinnable
coating systems, or for coating pigments in aqueous suspension
following the pigment synthesis, it is preferred to use solvents
which are totally or partly water-dilutable. Where the products are
to be used, for example, in applications where the presence of VOCs
(volatile organic compounds) is unwanted, the formulation should as
far as possible be solvent-free or in appropriately high-boiling
carrier media.
[0105] Depending on the field of application it is possible for the
solvents used for the synthesis to remain in the reaction mixture,
or they are fully or partly removed and, where appropriate,
replaced by other solvents or carrier media. Depending on
compatibility the addition compounds of the invention can also be
combined with resins, resin solutions, reactive diluents, binders
or other prior art additives, such as other wetting agents and
dispersants, anti-settling agents, surface-active additives such as
silicones, for example, and the like.
[0106] The solvent can be removed, for example, by distillation,
where appropriate under reduced pressure, and/or azeotropically
with the addition of water, such removal being complete or partial.
Alternatively the active substance can be isolated by
precipitation, by the addition of non-solvents such as aliphatic
hydrocarbons, hexane for example, subsequent separation by
filtration, and drying if desired. The active substance obtained by
one of these methods can then be diluted in a solvent suitable for
the particular field of application, or where appropriate can be
used as it is, in the case of powder coating materials for example.
If desired, following the addition of suitable high-boiling
solvents, the solvent in which the addition product is dissolved
can be distilled off, where appropriate under reduced pressure,
and/or azeotropically with addition of water, and in this way the
addition product can be transferred to a carrier medium that is
suitable for the respective field of application.
[0107] The reactions can be carried out in the presence of
customary catalysts, examples being organotin compounds, such as
dibutyltin dilaurate, other organometallic compounds such as iron
acetylacetonate, tertiary amines such as triethylenediamine,
enzymes or the like.
[0108] By varying the substituents of the formula (Ia) in terms of
the nature, proportions and/or molecular weights thereof, it is
possible to adapt the properties of the addition compounds of the
invention to the different fields of application. For example, the
solubility and compatibility can be brought into line with a very
wide variety of solvents, carrier media, binders, resins, solids
and, where appropriate, further polymeric compounds that are
present in coating and moulding materials in which the addition
compounds according to the invention are employed.
[0109] For use in highly polar systems such as water-based coating
materials, for example, the radicals Y ought to include a
sufficiently high fraction of polar groups, such as polyethylene
oxides, for example, in order to achieve a level of water
solubility which is sufficient for the particular area of use. This
fraction of hydrophilic groups ought also not to be too high,
however, if in certain applications this results in an unwanted
increase in the sensitivity to water. In one important embodiment
the radicals Y of the XH-functionalized polyalkylene oxides are
radicals which endow the compounds Y--XH and also, ultimately, the
addition compounds of the invention essentially with insolubility
in water. Such radicals Y of the XH-functionalized polyalkylene
oxides advantageously contain up to a maximum of 28% by weight,
preferably up to a maximum of 20% by weight, more preferably up to
a maximum of 10% by weight and very preferably up to a maximum of
5% by weight of ethylene oxide units, based on the total amount of
alkylene oxide units in the radical Y.
[0110] In the case of use in apolar systems such as long-oil alkyd
paints, PVC plastisols or polyolefins there should preferably be an
appropriate fraction of apolar groups, and in the case of use in
systems where broad compatibility is important, such as pigment
concentrates, for example, a balanced combination of polar and
apolar groups is of advantage.
[0111] For dispersing in silicone oils such as
decamethylcyclopentasiloxane, for example, for cosmetic
preparations for example, polydimethylsiloxane-containing addition
compounds in particular are suitable. If the addition compounds are
used, for example, in a polyurethane resin or in a coating material
whose binder is a polyurethane it is advantageous to use those
addition compounds of the invention whose molecule, by virtue of
the groups present in the starting compounds of the formulae (Ia)
and (Ib), also includes urethane groups or similar groups which, as
is known to the skilled person, are compatible with polyurethanes.
The same applies, mutatis mutandis, to, for example, polyacrylates,
polyesters, alkyd resins, and other polymers.
[0112] Mutatis mutandis this also applies to the substituents of
components (c1) and (c2), which are of particular influence on the
affinity of the addition compounds of the invention for the solids
used that are to be dispersed.
[0113] Addition compounds of the invention with surface-active
substituents may modify the surface tension of the substrates
produced using them. If, for instance, very apolar groups such as
long-chain alkyl groups having more than 12 carbon atoms,
polydimethylsiloxane-containing and/or perfluoroalkyl-containing
groups are present, for example, the products are suitable for
reducing the surface tension of liquid organic or aqueous systems
or of solid systems, and for influencing the associated properties
such as, for example, wetting properties, stainability,
printability, flow and foam behaviour. In systems which exhibit
reactivity with OH groups, COOH groups and/or double bonds,
examples being 2-component systems based on isocyanate or on
melamine resin, epoxide-containing systems, radiation-curing
coatings, such as UV-curing or electron-beam-curing paints and
printing inks, or unsaturated polyester systems, for example,
co-crosslinking can be achieved through the use of addition
compounds of the invention containing reactive groups such as OH
groups, COOH groups and/or unsaturated groups, and leads to
improvements in adhesion, incorporation of solids, mechanical
properties and migration behaviour. In applications where the
presence of double bonds leads to unwanted disadvantages such as
discoloration, as a result for example of high processing
temperatures, it is advantageous to use addition compounds of the
invention with as few unsaturated groups as possible and preferably
none at all.
[0114] The number-average molecular weight M.sub.n of the addition
compounds of the invention is preferably at least 500 g/mol, more
preferably at least 800 g/mol, very preferably at least 1200 g/mol
and ideally at least 2000 g/mol.
[0115] The invention also provides a process for preparing the
addition compounds of the invention, which comprises reacting
[0116] (a) one or more polyisocyanates having at least two
isocyanate groups per molecule with [0117] (b1) one or more
compounds of the formula (Ia)
[0117] Y--XH (Ia) [0118] where [0119] XH is a group that is
reactive towards isocyanates and [0120] Y is a monomeric or
polymeric group that is not reactive towards isocyanates, that
contains no tertiary amino groups and that comprises one or more
aliphatic, cycloaliphatic and/or aromatic groups, [0121] the
compound of the general formula (Ia) possessing a number-average
molar mass M.sub.n of less than 20 000 g/mol and [0122] at least 55
mol % of the compounds of the formula (Ia) possessing a
number-average molecular weight M.sub.n of 150 to 10 000 g/mol
[0123] and which represent XH-functionalized polyalkylene oxides
which contain 40 to 100 mol % of alkylene oxide units having at
least three carbon atoms, based on the total amount of alkylene
oxide units, [0124] with the proviso that 20% to 90% of the
isocyanate groups of component (a) are reacted with the compounds
of the formula (Ia), [0125] (b2) one or more compounds of the
formula (Ib)
[0125] G-(XH), (Ib) [0126] where n is 2 to 4 and G is an aliphatic,
cycloaliphatic and/or aromatic group which contains at least 2
carbon atoms, has no tertiary amino groups and has a number-average
molecular weight M.sub.n of not more than 3000, and which can
contain --O--, --COO--, --CONH--, --S-- and/or --SO.sub.2-- groups,
are reacted in an amount such that 0% to 60%, preferably 0 to 45%
and more preferably 0 to 40% of the NCO groups of the
polyisocyanates originally used are reacted, [0127] with the
proviso that, as a result of the reactions (b1) and (b2), a total
of at least 20% and not more than 90%, preferably 30 to 65% and
more preferably 40 to 60% of the isocyanate groups of the
polyisocyanates originally used have undergone reaction, and [0128]
(c1) one or more compounds of the general formula (IIa)
[0128] Z-Q (IIa) [0129] in which Q is --NH.sub.2, --NHR or OH, in
which R is a linear or branched alkyl group having 1 to 18 carbon
atoms, and [0130] Z is an organic basic radical having at least one
tertiary amino group and containing no isocyanate-reactive groups,
and [0131] (c2) optionally one or more compounds of the general
formula (IIb)
[0131] M-Q (IIb) [0132] in which Q is --NH.sub.2, --NHR or OH, in
which R is a linear or branched alkyl group having 1 to 18 carbon
atoms, and [0133] M is an organic radical having a number-average
molar mass of not more than 1000 g/mol, with at least one tertiary
amino group and at least one hydroxyl group, [0134] with the
proviso that at least 10% of the isocyanate groups of component (a)
are reacted with component (c1).
[0135] The components (a), (b1), (b2), (c1) and (c2) that are used
in the process of the invention correspond to those already
described earlier on above.
[0136] The process of the invention is preferably carried out such
that first of all the compounds of component (a) are reacted with
those of component (b1) and, if used, (b2) and only then are the
remaining isocyanate groups reacted with the compounds of component
(c1).
[0137] It is further advantageous, first to react the compounds of
the formula (Ia) of component (b1) with the polyisocyanate
component (a) and only then to carry out a reaction with the
compounds of the formula (Ib) of component (b2).
[0138] The invention further provides for the use of the
above-described addition compounds of the invention as wetting
agents and dispersants and as dispersion stabilizers.
[0139] The invention further provides pulverous or fibrous solids
intended for incorporation into liquid systems and coated with
these addition compounds as dispersants and as dispersion
stabilizers or as wetting agents.
[0140] The addition compounds of the invention can be used in
dispersants, dispersion stabilizers or wetting agents in place of
their prior art counterparts. Thus, for example, they can be used
in the preparation or processing of paints, printing inks, other
inks, for example inkjet inks, paper coatings, leather and textile
colours, pastes, pigment concentrates, ceramics, and cosmetic
preparations, particularly if they contain solids such as pigments
and/or fillers. They can also be employed in connection with the
preparation or processing of moulding compositions based on
synthetic, semi-synthetic or natural macromolecular substances,
such as polyvinyl chloride, saturated or unsaturated polyesters,
polyurethanes, polystyrenes, polyacrylates, polyamides, epoxy
resins, polyolefins such as polyethylene or polypropylene, for
example. By way of example it is possible to use the addition
compounds for preparing casting compositions, PVC plastisols,
gelcoats, polymer concrete, printed circuit boards, industrial
paints, wood and furniture varnishes, vehicle finishes, marine
paints, anti-corrosion paints, can coatings and coil coatings,
decorating paints and architectural paints, where binders and/or
solvents, pigments and optionally fillers, the addition compound,
and typical auxiliaries are mixed.
[0141] The addition compounds are used preferably for producing
pigment- and/or filler-comprising pigment concentrates, paints,
pastes and/or moulding compositions.
[0142] Examples of typical binders are resins based on
polyurethanes, cellulose nitrates, cellulose acetobutyrates,
alkyds, melamines, polyesters, chlorinated rubbers, epoxides and
acrylates. Examples of water-based coatings are cathodic or anodic
electrodeposition coatings for car bodies, for example. Further
examples are renders, silicate paints, emulsion paints, aqueous
paints based on water-dilutable alkyds, alkyd emulsions, hybrid
systems, 2-component systems, polyurethane dispersions and acrylate
dispersions.
[0143] The addition compounds of the invention are particularly
suitable as well for preparing concentrates of solids, such as
pigment concentrates, for example. For that purpose the compounds
of the invention are initially introduced in a carrier medium such
as organic solvents, plasticizers and/or water, and the solids to
be dispersed are added with stirring. Additionally these
concentrates may include binders and/or other auxiliaries. With the
addition compounds of the invention, however, it is possible in
particular to prepare stable binder-free pigment concentrates. It
is also possible using the compounds of the invention to prepare
fluid concentrates of solids from pigment presscakes. In this case
the compound of the invention is admixed to the presscake, which
may additionally contain organic solvents, plasticizers and/or
water, and the resulting mixture is dispersed. Prepared in their
different ways, the concentrates of solids can then be incorporated
into different substrates such as, for example, alkyd resins,
polyester resins, acrylate resins, polyurethane resins or epoxy
resins. Pigments can also, however, be dispersed directly in the
addition compounds of the invention, without solvent, and are then
particularly suitable for pigmenting thermoplastic and thermoset
polymer formulations.
[0144] The addition compounds of the invention can also be used
with advantage in connection with the production of colour filters
for liquid-crystal displays, liquid-crystal screens, colour
resolution devices, sensors, plasma screens, displays based on SED
(Surface conduction Electron emitter Display) and for MLCC
(Multi-Layer Ceramic Compounds). The MLCC technology is used in
connection with the production of microchips and printed circuit
boards.
[0145] The addition compounds of the invention can also be used to
produce cosmetic preparations such as, for example, makeup, powder,
lipsticks, hair colorants, creams, nail varnishes and sun
protection products. These may be present in the customary forms,
as for example W/O or O/W emulsions, solutions, gels, creams,
lotions or sprays. The addition compounds of the invention can be
used with advantage in dispersions that are used for preparing
these preparations. These dispersions may contain the carrier media
that are typical for these purposes in cosmetology, such as, for
example, water, castor oils or silicone oils, and solids, such as
organic and inorganic pigments such as titanium dioxide or iron
oxide, for example.
[0146] The invention also provides, furthermore, for the use of an
addition compound of the invention for preparing a pigmented paint
which serves in particular for producing a pigmented coating on a
substrate, the pigmented paint being applied to the substrate and
the pigmented paint which has been applied to the substrate being
baked or cured and/or crosslinked.
[0147] The dispersants can be used alone or together with customary
prior art binders. For use in polyolefins, for example, it can be
advantageous to use corresponding polyolefins of low molecular mass
as carrier materials, together with the dispersant.
[0148] One inventive use of the addition compounds is in the
preparation of dispersible solids in powder particle and/or fibre
particle form, particularly of dispersible pigments or plastics
fillers, the particles being coated with the inventive addition
compound. Coatings of this kind of organic and inorganic solids are
performed in a known way, as described in EP-A-0 270 126, for
example. In this case the solvent or emulsion medium can either be
removed or remain in the mixture, with the formation of pastes.
These pastes are customary commercial products and may additionally
include binder fractions and also further auxiliaries and
additives. Specifically in the case of the pigments it is possible
for the pigment surface to be coated during or after the synthesis
of the pigments, by the addition, for example, of the addition
products of the invention to the pigment suspension or during or
after the pigment finish. The pigments pretreated in this way are
distinguished by greater ease of incorporation and also by improved
viscosity, flocculation and gloss behaviour and by higher colour
strength as compared with untreated pigments.
[0149] Besides the above-described application, as dispersants
and/or coating materials for pulverous and fibrous solids, the
addition compounds of the invention can also be used as viscosity
reducers and compatibilizers in synthetic resins. Examples of such
synthetic resins are those known as sheet moulding compounds (SMC)
and bulk moulding compounds (BMC), which are composed of
unsaturated polyester resins with high filler and fibre contents.
Their preparation and processing are described by way of example in
DE-A-36 43007. One problem affecting SMC and BMC synthetic resin
mixtures is that often polystyrene (PS) is added to the formulation
in order to reduce contraction during the processing operation. PS
is not compatible with the unsaturated polyester resins used, and
separation of the components occurs. When PS-filled SMC or BMC
mixtures are being used, the additives of the invention, by virtue
of their good dispersing qualities, are able to bring about
compatibilization between PS and unsaturated polyester resin,
thereby increasing the storage stability and processing reliability
of such mixtures.
[0150] In many cases, including for example in incompatible polyol
mixtures, polyol/isocyanate mixtures or polyol/blowing agent
mixtures used for polyurethane production, through the addition
compounds of the invention it is possible wholly or partly to
prevent the separation problems which result from this
incompatibility and affect dispersions, especially emulsions.
[0151] The addition compounds of the invention are added preferably
in an amount of 0.01% to 10% by weight, based on the total
formulation amount. Based on the solid to be dispersed, they are
used in an amount of preferably 0.5% to 100% by weight. Where
difficult-to-disperse solids are used, the amount of inventive
addition compound employed may well be higher. The amount of
dispersant is generally dependent on the surface that is to be
coated of the substance that is to be dispersed. For example, if
titanium dioxide is used as a pigment, the amount of dispersant is
lower than in the case of, say, carbon black. Generally speaking,
the amount of dispersant needed to disperse inorganic pigments is
less than for organic pigments, since the latter have a higher
specific surface area and, consequently, a greater amount of
dispersant is needed. Typical addition levels for inorganic
pigments are 1-10% by weight, for organic pigments 10-30% by weight
(in each case expressed as active substance of addition compound
relative to pigment). In the case of very finely divided pigments
(e.g. some carbon blacks), amounts of 30-80% by weight or more need
to be added, even.
[0152] As a criterion of sufficient pigment stabilization it is
possible for example to employ colour strength, gloss and
transparency of the pigment dispersion or the degree of floating
(rub-out test) in the case of a white reduction.
[0153] The dispersing of the solids may take place as a single
dispersion or else as a mixed dispersion with two or more pigments
simultaneously, the best results generally being achievable with
single dispersions. When mixtures of different solids are used,
opposing charges on the surfaces of the solids may result in an
increased incidence of agglomeration in the liquid phase. In these
cases it is frequently possible, using the addition compounds of
the invention, to achieve a charge of equal sign, generally a
positive charge, for all of the particles and hence to avoid
instabilities due to charge differences. The dispersants achieve
their optimum effect when added to the millbase, particularly if
first of all the solid to be dispersed is mixed only with the
additive and, where appropriate, solvents ("premix"), since in that
case the additive is able to adsorb preferentially onto the surface
of the solid, without having to compete with the binder polymers.
In practice, however, this procedure is necessary only in
exceptional cases. If necessary, the addition compounds can also be
employed subsequently (as what are called "post-additives"), in
order, for example, to solve floating or flocculation problems in a
batch which has already been let down. Generally speaking, however,
increased levels of addition of additive are necessary in this
case.
[0154] In certain cases the addition compounds of the invention may
exert a more or less pronounced influence on the rheology of the
system. In such cases, therefore, they can also be used for
rheology control, where appropriate in combination with other
rheological additives such as fumed silica, phyllosilicates
(bentonites), hydrogenated castor oils, or the additives
BYK.RTM.-410, BYK.RTM.-420 and BYK.RTM.-425 (BYK Chemie GmbH). In
these cases, synergistic effects are frequently observed. In many
cases it is also possible to improve the corrosion control
properties of coatings through the use of the addition compounds of
the invention.
[0155] Examples of pulverous or fibrous solids are those which may
be coated with dispersants, especially organic and inorganic
pigments which are used in paints, coating materials, moulding
compositions or other plastics, and organic or inorganic fillers
which are used to fill or reinforce paints, coating materials,
moulding compositions or other plastics. A subgroup of such fillers
are fibres of organic and/or inorganic type which are likewise used
as fillers or reinforcing substances.
[0156] Examples of pigments are mono-, di-, tri- and poly-azo
pigments, oxazine, dioxazine and thiazine pigments,
diketopyrrolopyrroles, phthalocyanines, ultramarine and other metal
complex pigments, indigoid pigments, diphenylmethane,
triarylmethane, xanthene, acridine, quinacridone and methine
pigments, anthraquinone, pyranthrone, perylene and other polycyclic
carbonyl pigments, inorganic pigments based on carbon black,
graphite, zinc, titanium dioxide, zinc oxide, zinc sulphide, zinc
phosphate, barium sulphate, lithopones, iron oxide, ultramarine,
manganese phosphate, cobalt aluminate, cobalt stannate, cobalt
zincate, antimony oxide, antimony sulphide, chromium oxide, zinc
chromate, mixed metal oxides based on nickel, bismuth, vanadium,
molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron,
chromium, antimony, magnesium, aluminium (for example nickel
titanium yellow, bismuth vanadate, molybdate yellow or chromium
titanium yellow), magnetic pigments based on pure iron, iron oxides
and chromium oxides or mixed oxides, metallic pigments comprising
aluminium, zinc, copper or brass, and also pearlescent pigments,
and fluorescent and phosphorescent luminescent pigments. All of the
afore-mentioned pigments may be in surface-modified form and may
possess basic, acidic or neutral groups on the surface. Preference
is given to neutral or acidically modified pigments, such as
oxidized carbon blacks, for example.
[0157] Further examples are nanoscale organic or inorganic solids
having particle sizes below 100 nm, such as certain grades of
carbon black, or particles composed of a metal or semimetal oxide
or hydroxide, and also particles composed of mixed metal and/or
semimetal oxides and/or hydroxides. By way of example it is
possible to employ the oxides and/or oxide hydroxides of aluminium,
silicon, zinc, titanium, etc. in order to prepare extremely finely
divided solids of this kind. These oxidic, hydroxidic or
oxide-hydroxidic particles may be prepared by any of a wide variety
of methods such as, for example, ion-exchange operations, plasma
operations, sol-gel processes, precipitation, comminution (by
grinding, for example) or flame hydrolysis, and the like.
[0158] Examples of pulverous or fibrous fillers are, for example,
those composed of pulverous or fibrous particles of aluminium
oxide, aluminium hydroxide, silicon dioxide, kieselguhr, siliceous
earth, quartz, silica gel, talc, kaolin, mica, perlite, feldspar,
slate flour, calcium sulphate, barium sulphate, calcium carbonate,
calcite, dolomite, glass or carbon. Further examples of pigments or
fillers are found for example in EP-A-0 270 126. Additionally flame
retardants such as, for example, aluminium hydroxide or magnesium
hydroxide, and matting agents such as silicas, for example, can
likewise be dispersed and stabilized outstandingly.
[0159] In the text below, the present invention is further
illustrated by examples which follow.
EXAMPLES
[0160] In the case of substances without molecular uniformity the
stated molecular weights--below as already in the foregoing
description--represent average values of the numerical mean. The
molecular weights or number-average molecular weights M.sub.n, are
determined, when titratable hydroxyl or amino groups are present,
by end-group determination via the determination of the OH number
or amine number, respectively. In the case of compounds to which an
end-group determination cannot be applied, the number-average
molecular weight is determined by means of gel permeation
chromatography against a polystyrene standard.
[0161] Unless otherwise remarked, parts are parts by weight and
percentages are percentages by weight.
[0162] The free NCO content of the polyisocyanates employed and
also the course of the NCO addition reactions, are determined in
accordance with EN ISO 9369 by reaction with butylamine and
subsequent titration of the amine excess. These methods are also
described in Saul Patai's "The Chemistry of Cyanates and their Thio
Derivatives", Part 1, Chapter 5, 1977.
[0163] The hydroxy-functional caprolactone polyesters are prepared
as described in EP 158678, for example.
PREPARATION EXAMPLES
Example 1
Non-Inventive, Comparative Example
[0164] 28.1 parts of polyisocyanate P1 are homogenized with 38.5
parts of BCPE1100 and 22.7 parts of PMA (methoxypropyl acetate).
The mixture is heated to 80.degree. C. under inert gas, and 0.003
part of DBTL (dibutyltin dilaurate) is added. The mixture is
stirred at this temperature for about an hour until 65% of the NCO
groups used have undergone reaction. Then 2 parts of DMAPA are
added and stirring is continued at 80.degree. C. until all of the
NCO groups have been consumed by reaction. The product is of medium
viscosity, and has a solids content of 60% and an amine number of
12 mg KOH/g. After a few days at 20.degree. C. the product shows
strong formation of crystals.
[0165] In aromatic-free white spirit the product is insoluble.
Example 2
[0166] In analogy to Example 1, 38.5 parts of BPO1100 are used
instead of BCPE1100. The solids content is 60% and the amine number
is 12 mg KOH/g. On storage, the product remains homogeneous and
liquid. Even on prolonged storage below 0.degree. C. there is no
crystal formation.
[0167] In aromatic-free white spirit it is possible to prepare a
clear, 10% solution.
Example 3
[0168] In analogy to Example 2, 1.7 parts of DMEA are used instead
of DMAPA. The solids content is 60% and the amine number is 12 mg
KOH/g.
Example 4
[0169] In analogy to Example 2, 2.5 parts of API are used instead
of DMAPA. The solids content is 60% and the amine number is 12 mg
KOH/g.
Example 5
[0170] In analogy to Example 2, 2.3 parts of DEEA are used instead
of DMAPA. The solids content is 60% and the amine number is 12 mg
KOH/g.
Example 6
[0171] 15.7 parts of polyisocyanate P1 are homogenized with 9.9
parts of BPO1100 and 46.9 parts of PMA. The mixture is heated to
60.degree. C. under inert gas, and 0.001 part of DBTL is added.
After about an hour, 30% of the NCO groups used have undergone
reaction. Then 1.3 parts of a PEG400 are added. Stirring is
continued at 60.degree. C. until a further 21% of the NCO groups
used have undergone reaction. Then 1.9 parts of API and 24.5 parts
of N-methylpyrrolidone are added and stirring is continued at
80.degree. C. until the remaining NCO groups have been consumed by
reaction. The product possesses an amine number of 8 mg KOH/g and a
solids of 23%.
Example 7
[0172] 15.7 parts of polyisocyanate P1 are homogenized with 9.9
parts of BPO1100 and 46.9 parts of PMA. The mixture is heated to
60.degree. C. under inert gas, and 0.001 part of DBTL is added.
After about an hour, 30% of the NCO groups used have undergone
reaction. Then 3.15 parts of a PEG1000 are added. Stirring is
continued at 60.degree. C. until a further 21% of the NCO groups
used have undergone reaction. Then 1.9 parts of API and 24.5 parts
of N-methylpyrrolidone are added and stirring is continued at
80.degree. C. until the remaining NCO groups have been consumed by
reaction. The product possesses an amine number of 8 mg KOH/g and a
solids of 23%.
Example 8
[0173] 24 parts of polyisocyanate P1 are homogenized with 25.6
parts of BPO1400 and 26 parts of PMA and 41.3 parts of ethyl
acetate. The mixture is heated to 65.degree. C. under inert gas,
and 0.002 part of DBTL is added. After an hour, 40% of the NCO
groups used have undergone reaction. Then 1.5 parts of a PEG600 are
added. Stirring is continued at 65.degree. C. until a further 11%
of the NCO groups used have undergone reaction. Then 2.3 parts of
DMAPA are added and stirring is carried out at 70.degree. C. until
the remaining NCO groups have been consumed by reaction. The
product is of low viscosity and possesses a solids content of 35%
and an amine number of 10 mg KOH/g.
Example 9
[0174] 29.6 parts of polyisocyanate P1, 26.2 parts of ethyl acetate
and 0.001 part of DBTL are admixed slowly dropwise over an hour at
80.degree. C. with 24 parts of BPO700. When 60% of the NCO groups
used have been consumed by reaction, 2.7 parts of DMEA are added.
When the remaining NCO groups have been consumed by reaction, the
batch is diluted with 17.4 parts of propylene glycol monomethyl
ether (PM). The product is of medium viscosity and possesses a
solids content of 43% and an amine number of 11 mg KOH/g.
Example 10
[0175] 29.6 parts of polyisocyanate P1, 50 parts of PMA and 0.001
part of DBTL are admixed slowly dropwise over an hour at 80.degree.
C. with 37.2 parts of BPO1100. When 60% of the NCO groups used have
been consumed by reaction, 2.3 parts of DMAPA are added. When the
remaining NCO groups have been consumed by reaction, the batch is
diluted with 17.4 parts of tripropylene glycol monomethyl ether
(TPM). The product is of medium viscosity and possesses a solids
content of 40% and an amine number of 9 mg KOH/g.
Example 11
[0176] 29.6 parts of polyisocyanate P1, 65.3 parts of PMA and 0.001
part of DBTL are admixed slowly dropwise over an hour at 80.degree.
C. with 47.4 parts of BPO1400. When 60% of the NCO groups used have
been consumed by reaction, 2.3 parts of DMAPA are added. When the
remaining NCO groups have been consumed by reaction, the batch is
diluted with 17.4 parts of dipropylene glycol monomethyl ether
(DPM). The product is of medium viscosity and possesses a solids
content of 40% and an amine number of 8 mg KOH/g.
Example 12
[0177] 29.6 parts of polyisocyanate P3, 80.4 parts of PMA and 0.001
part of DBTL are admixed slowly dropwise over an hour at 80.degree.
C. with 57.5 parts of BPO1700. When 60% of the NCO groups used have
been consumed by reaction, 2.3 parts of DMAPA are added. When the
remaining NCO groups have been consumed by reaction, the batch is
diluted with 17.4 parts of dipropylene glycol monomethyl ether
(DPM). The product is of medium viscosity and possesses a solids
content of 40% and an amine number of 7 mg KOH/g.
Example 13
[0178] 14.4 parts of polyisocyanate P2, 37 parts of PMA and 0.003
part of DBTL are admixed slowly dropwise over 4 hours at 80.degree.
C. with 41 parts of BPO1100. When 50% of the NCO groups used have
been consumed by reaction, 4.7 parts of API are added. When the
remaining NCO groups have been consumed by reaction, the batch is
diluted with 3 parts of dipropylene glycol monomethyl ether (DPM).
The product is of medium viscosity and possesses a solids content
of 60% and an amine number of 21 mg KOH/g.
Key:
[0179] P1=aromatic TDI polyisocyanurate having a free NCO content
of 8.0% as a 51% strength solution in butyl acetate, e.g.
Desmodur.RTM. IL, Bayer AG [0180] P2=aliphatic polyisocyanate (HDI
trimer) having a free NCO content of 21.8%, e.g. Desmodur.RTM.
N3300, Bayer AG [0181] P3=aromatic TDI polyisocyanurate having a
free NCO content of 8.0%; as a 51% strength solution in ethyl
acetate, e.g. Desmodur.RTM. IL EA, Bayer AG [0182]
BCPE1100=monohydroxy-functional .epsilon.-caprolactone polyester,
prepared starting from butanol, average molecular weight Mn 1100
[0183] BPO700, 1100, 1400=monohydroxy-functional PO polyether,
prepared starting from butanol, average molecular weight Mn=700,
1100 or 1400 [0184] PEG 400, 600, 1000=polyethylene glycol
(dihydroxy-functional), average molecular weight Mn 400, 600 or
1000 [0185] DMEA=N,N-dimethylaminoethanol [0186]
API=aminopropylimidazole [0187] DEEA=N,N-diethylaminoethanol [0188]
DMAPA=N,N-dimethylaminopropane
USE EXAMPLES
Use in Paste System
TABLE-US-00001 [0189] Pigment paste with Spezialschwarz 4: Laropal
A81 65% strength in PMA 23.50 parts PMA 22.90 parts Inventive
addition compound 19.60 parts Carbon black, e.g. Spezialschwarz 4
34.00 parts (Degussa AG) 100.00 parts +10% PMA
Dispersion: Dispermat CV/60 min/10 000 rpm/40.degree. C./1 mm beads
1:1
[0190] Pigment paste Spezialschwarz 4, prepared with Examples 2, 3
and 4
TABLE-US-00002 Evaluation of paste viscosity-visual: Additive:
Evaluation: Example 2 1 Example 3 2 Example 4 1 Rating: 1 = low
viscosity, 3 = medium viscosity, 5 = pasty
* * * * *